CN102730713A - Ionothermal preparation method for rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 - Google Patents
Ionothermal preparation method for rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 Download PDFInfo
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Abstract
The invention provides an ionothermal preparation method for a rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7. The method comprises the steps of preparation of a eutectic mixture, preparation of a rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 precursor and preparation of the rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7. According to testing results, the X-ray diffraction pattern of the rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 synthesized by using the preparation method provided in the invention is identical with the standard diffraction pattern of a ZON-structured molecular sieve UiO-7, and the rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 has high crystallinity; according to results of scanning electron microscopy, crystals of the rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 are of a uniform particle size and have an integral structure; a thermal analyzer, an N2 adsorption BET specific surface area analyzer and a pore size analyzer are used for testing the thermal stability and pore structure of a product, and it is proved that the rare earth-substituted ZON-structured aluminophosphate molecular sieve UiO-7 has high thermal stability, an improved specific surface area and an improved pore volume. The preparation method provided in the invention has the advantages of high safety, low toxicity, low cost, convenient operation, capacity of preparing a product with high crystallinity.
Description
Technical field
The invention belongs to the material technology field, be specifically related to the ion process for thermosynthesizing of a kind of ZON structure rare-earth heteroatoms phosphate aluminium molecular sieve Me-UiO-7.
Background technology
The patent No. by U.S. combinating carbide company (UCC) application is in the USP of US 4310440, has synthesized one type of brand-new molecular sieve family-aluminium phosphate molecular sieve and verivate thereof series (AlPO
4-n, n representative structure model), this is one type of not siliceous molecular sieve, its structure mainly is made up of aluminum-oxygen tetrahedron and phosphorus oxygen tetrahedron.2004; Professor R.E.Morris of Britain St Andrews university waits and at first on Nature, has reported the research that utilizes the synthetic microporous aluminium phosphate molecular sieve material of ionic liquid, has formed a kind of brand-new molecular sieve compound method-ion thermal synthesis method (Ionothermal synthesis).Compare with traditional solid or fluent material, ionic liquid has some unique physics and chemical property and functions peculiar, like low saturated vapor pressure, lower melting point, high polarity, non-volatile and high thermostability or the like.Its unique character of ion liquid these function endowings does not also replace in synthesizing of ZON structure phosphate aluminium molecular sieve Ui O-7 at rare earth and uses.
Publication number is the Chinese patent of CN101468318A, discloses rare-earth-containing molecular sieve catalyst of modification and preparation method thereof, is crystal seed with the ZSM-5 molecular sieve that contains rare earth, and said crystal seed contains rare earth oxide Ce
2O
3And La
2O
3Select water glass or sodium silicate aqueous solution as the silicon source; Aluminum sulfate aqueous solution, the aluminum chloride aqueous solution or aluminium phosphate aqueous solution are as the aluminium source; Utilize pH value to 10～12,150～200 ℃ airtight heating 20～40 hours of mineral acid regulation system such as phosphoric acid or sulfuric acid, obtain containing the sodium type ZSM-5 molecular sieve of rare earth.
After the opening that battle-axe used in ancient China is big cerous nitrate and lanthanum nitrate hexahydrate and SAPO-11 molecular sieve powder are mixed of University Of Tianjin, make rare earth modified SAPO-11 molecular sieve through ion exchange method and pickling process.
The skeleton of aluminium phosphate molecular sieve is electroneutral; Do not have
acidic site center, limited the application of aluminium phosphate molecular sieve at catalytic field.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming that above-mentioned hydrothermal method synthesizing rare-earth replaces ZON structure phosphate aluminium molecular sieve UiO-7, provides the high and low toxicity of a kind of degree of safety, low cost, easy to operate rare earth to replace the ion hot preparation method of ZON structure phosphate aluminium molecular sieve UiO-7.
Addressing the above problem the technical scheme that is adopted comprises the steps:
1, preparation eutectic mixture
Tetramethyl ammonium chloride is mixed in beaker for 1:0.36～0.67 with imidazoles in molar ratio, place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture.
2, the preparation rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7 presoma
With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:1.5～3:0.2～1.5:0.02～0.18 stirs in beaker; Move in the teflon-lined reaction kettle; 150～200 ℃ of crystallization of normal pressure 16～96 hours; Be cooled to room temperature, be prepared into the hetero-atom molecular-sieve presoma.
Above-mentioned rare earth nitrate is any one in cerous nitrate, neodymium nitrate, the Lanthanum trinitrate.
3, the preparation rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7
The molecular sieve presoma is filtered with B, use deionized water, ethanol, the ultrasonic repetitive scrubbing of acetone respectively 3～5 times, air-dry in the air, be prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7.
In preparation eutectic mixture step 1 of the present invention; Is that 1:0.4～0.6 beaker in mix with imidazoles by preferred molar ratio with tetramethyl ammonium chloride; Place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture.Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; Is that 1:30:1.5～2.5:0.5～1.2:0.08～0.15 stirs in beaker with aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate by preferred molar ratio; Move in the teflon-lined reaction kettle; 160～180 ℃ of crystallization of normal pressure 24～72 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
In preparation eutectic mixture step 1 of the present invention; Is that 1:0.5 beaker in mix with imidazoles by optimum mole ratio with tetramethyl ammonium chloride; Place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture.Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; Is that 1:30:2:1.0:0.1 stirs in beaker with aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate by optimum mole ratio; Move in the teflon-lined reaction kettle; The best 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
4, detect
Adopt x-ray diffractometer, N
2Diffuse spectrometer, thermal analyzer of absorption BET specific surface area appearance and aperture analyser, ultraviolet-visible characterizes structure and the thermostability for preparing product, and environmental scanning electronic microscope is observed the surface topography of molecular sieve.
The present invention adopts ion process for thermosynthesizing direct crystallization to prepare rare earth replacement ZON structure phosphate aluminium molecular sieve UiO-7, has overcome the synthetic shortcoming that SF is low, toxicity is high of the synthetic heteroatom phosphate aluminium molecular sieve of hydrothermal method.Adopt the inventive method synthetic rare earth to replace ZON structure phosphate aluminium molecular sieve UiO-7, with the X-ray diffractometer test, the diffracting spectrum of X ray diffracting spectrum and ZON structure aluminium phosphate molecular sieve UiO-7 standard is consistent, and crystalline percent crystallinity is higher; Use scanning electron microscopic observation, crystal particle diameter size homogeneous, structural integrity have regular appearance.The present invention has the high and low toxicity of degree of safety, low cost, easy to operate, prepared rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7 percent crystallinity advantages of higher, can be used for preparing rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Description of drawings
Fig. 1 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the X ray diffracting spectrum of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.1.
Fig. 2 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the X ray diffracting spectrum of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.1.
Fig. 3 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the X ray diffracting spectrum of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.1.
Fig. 4 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the X ray diffracting spectrum of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.02.
Fig. 5 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the X ray diffracting spectrum of the prepared CeUiO-7 molecular sieve of 1:30:2:1:0.08.
Fig. 6 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the X ray diffracting spectrum of the prepared CeUiO-7 molecular sieve of 1:30:2:1:0.15.
Fig. 7 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the X ray diffracting spectrum of the prepared CeUiO-7 molecular sieve of 1:30:2:1:0.18.
Fig. 8 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the X ray diffracting spectrum of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.02.
Fig. 9 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the X ray diffracting spectrum of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.08.
Figure 10 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the X ray diffracting spectrum of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.15.
Figure 11 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the X ray diffracting spectrum of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.18.
Figure 12 is the stereoscan photograph of pure phase ZON structure phosphate aluminium molecular sieve UiO-7.
Figure 13 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the stereoscan photograph of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 14 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the stereoscan photograph of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 15 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the stereoscan photograph of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 16 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the stereoscan photograph of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.02.
Figure 17 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the stereoscan photograph of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.08.
Figure 18 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the stereoscan photograph of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.15.
Figure 19 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the stereoscan photograph of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.18.
Figure 20 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the stereoscan photograph of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.02.
Figure 21 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the stereoscan photograph of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.08.
Figure 22 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the stereoscan photograph of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.15.
Figure 23 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the stereoscan photograph of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.18.
Figure 24 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the stereoscan photograph of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.02.
Figure 25 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the stereoscan photograph of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.08.
Figure 26 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the stereoscan photograph of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.15.
Figure 27 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the stereoscan photograph of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.18.
Figure 28 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the thermogravimetric spectrogram of the prepared Ce-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 29 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the thermogravimetric spectrogram of the prepared Nd-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 30 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the thermogravimetric spectrogram of the prepared La-UiO-7 molecular sieve of 1:30:2:1:0.1.
Figure 31 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Ce 3+Mol ratio be the ultraviolet-visible of the prepared Ce-UiO-7 molecular sieve of the 1:30:2:1:0.1 spectrogram that diffuses.
Figure 32 is n
Al 3+: n
EU: n
P 5+: n
F -: n
Nd 3+Mol ratio be the ultraviolet-visible of the prepared Nd-UiO-7 molecular sieve of the 1:30:2:1:0.1 spectrogram that diffuses.
Figure 33 is n
Al 3+: n
EU: n
P 5+: n
F -: n
La 3+Mol ratio be the ultraviolet-visible of the prepared La-UiO-7 molecular sieve of the 1:30:2:1:0.1 spectrogram that diffuses.
Embodiment
To further explain of the present invention, but the invention is not restricted to these embodiment below in conjunction with accompanying drawing and embodiment.
The ion hot preparation method that replaces ZON structure phosphate aluminium molecular sieve UiO-7 with the rare earth cerium is an example, and its step is following:
1, preparation eutectic mixture
The 2.86g tetramethyl ammonium chloride is mixed in beaker with the 0.89g imidazoles; The mol ratio of tetramethyl ammonium chloride and imidazoles is 1:0.5; Place the mortar ground and mixed even; Placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture, and using the fusing point appearance to survey fusing point is 54～56 ℃.
2, preparation rare earth cerium replaces ZON structure phosphate aluminium molecular sieve Ui O-7 presoma
3, preparation rare earth cerium replaces ZON structure phosphate aluminium molecular sieve Ui O-7
The molecular sieve presoma is filtered with B, use deionized water, ethanol, acetone respectively, supersound washing 3～5 times, air-dry in the air, be prepared into the rare earth cerium and replace ZON structure phosphate aluminium molecular sieve UiO-7.
4, detect
Rare earth cerium to preparation replaces ZON structure phosphate aluminium molecular sieve UiO-7 employing X-ray diffractometer, N
2Diffuse spectrometer, thermal analyzer of absorption BET specific surface area appearance and aperture analyser, ultraviolet-visible characterizes the structure and the thermostability of molecular sieve; Environmental scanning electronic microscope has carried out observation experiment to the surface topography that the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7, and various experiment situation are following:
(1) X-ray diffraction analysis
The X-ray diffraction spectrogram of prepared product is as shown in Figure 1.Visible by Fig. 1, the X ray diffracting spectrum of the X ray diffracting spectrum of product and ZON structure phosphate aluminium molecular sieve UiO-7 is consistent, and crystalline percent crystallinity is higher.
(2) environmental scanning electronic microscope is observed
The stereoscan photograph of prepared product is seen Figure 13.Visible by Figure 12, Figure 13, UiO-7 compares with ZON structure phosphate aluminium molecular sieve, and it is cubic column pattern that the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 crystal, and the interface is clear, and smooth surface has agglomeration.
(3) measurement the specific area and pore volume
The SSA-4200 type N that the rare earth cerium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 and the sale of ZON structure phosphate aluminium molecular sieve UiO-7 employing Beijing Bi Aode Electronic Arts Inc.
2Absorption BET specific surface area appearance and aperture analyser have carried out contrast test by the working method of instrument, and the specific surface area that the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 is 273.5m
2/ g, pore volume are 0.198cc/g, and the specific surface area of ZON structure phosphate aluminium molecular sieve UiO-7 is 212.8m
2/ g, pore volume are 0.166cc/g, and the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 to be compared with ZON structure phosphate aluminium molecular sieve UiO-7, and specific surface area and pore volume that the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 all increase to some extent.
(4) measure thermal stability
The rare earth cerium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 adopt the U.S.'s Pyri s-of TA company II structural synthesis thermal analyzer (TG-DTA), test by the working method of instrument, test result is seen Figure 28.Visible by Figure 28, the rare earth cerium replaces the better heat stability of ZON structure phosphate aluminium molecular sieve UiO-7, and the crystalline structure is subsided when temperature is elevated to 600 ℃, has 2 main zero-g periods in the whole warm area.
(5) the ultraviolet-visible spectrum analysis that diffuses
The rare earth cerium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 carried out the ultraviolet-visible spectrum analysis that diffuses, the result sees Figure 31.Visible by Figure 31, strong absorption peak appears in ultraviolet region 200～300nm, show that Doped Rare Earth metal heteroatom Ce has entered into the skeleton of aluminium phosphate molecular sieve.And do not have absorption peak behind the 300nm, then can get rid of the existence of the outer heteroatoms oxide compound of skeleton.Can prove thus,, can prepare the rare earth cerium and replace ZON structure phosphate aluminium molecular sieve UiO-7 through the part aluminium atom on the isomorphous substitution framework of molecular sieve.
Embodiment 2
The ion hot preparation method that replaces ZON structure phosphate aluminium molecular sieve UiO-7 with rare earth neodymium is an example, and its step is following:
1, preparation eutectic mixture
It is identical that present embodiment prepares used raw material of the step 1 of eutectic mixture and proportioning and embodiment 1.Other step is identical with embodiment 1, is prepared into eutectic mixture, and using the fusing point appearance to survey fusing point is 54～56 ℃.
2, the preparation rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve Ui O-7 presoma
Used cerous nitrate is replaced with equimolar neodymium nitrate, and other step in this step is identical with embodiment 1, is prepared into rare earth neodymium and replaces ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth neodymium and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Prepared rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7 and adopts diffuse spectrometer, thermal analyzer of X-ray diffractometer, N2 absorption BET specific surface area appearance and aperture analyser, ultraviolet-visible that the structure and the thermostability of molecular sieve are characterized; Environmental scanning electronic microscope has carried out observation experiment to the surface topography that rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7, and various experiment situation are following:
(1) X-ray diffraction analysis
The X-ray diffraction spectrogram of prepared product is as shown in Figure 2.Visible by Fig. 2, the X ray diffracting spectrum of the X ray diffracting spectrum of product and ZON structure phosphate aluminium molecular sieve UiO-7 is consistent, and crystalline percent crystallinity is higher.
(2) environmental scanning electronic microscope is observed
The stereoscan photograph of prepared product is seen Figure 14.Visible by Figure 12, Figure 14, UiO-7 compares with ZON structure phosphate aluminium molecular sieve, and it is that two ends are sharp-pointed that rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7 crystal, the leaf shape pattern of middle part broad, and the interface is clear, and surface ratio is more coarse, and is better dispersed.
(3) measurement the specific area and pore volume
The SSA-4200 type N that rare earth neodymium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 and the sale of ZON structure phosphate aluminium molecular sieve UiO-7 employing Beijing Bi Aode Electronic Arts Inc.
2Absorption BET specific surface area appearance and aperture analyser have carried out contrast test by the working method of instrument, and the specific surface area that rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7 is 264.3m
2/ g, pore volume are 0.191cc/g, and rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7 to be compared with ZON structure phosphate aluminium molecular sieve UiO-7, and specific surface area and pore volume that rare earth neodymium replaces ZON structure phosphate aluminium molecular sieve UiO-7 all increase to some extent.
(4) measure thermal stability
Rare earth neodymium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 adopt the U.S. Pyris-of TA company II structural synthesis thermal analyzer (TG-DTA), test by the working method of instrument, test result is seen Figure 29.Visible by Figure 29, rare earth neodymium replaces the better heat stability of ZON structure phosphate aluminium molecular sieve UiO-7, and the crystalline structure is subsided when temperature is elevated to 600 ℃, has 2 main zero-g periods in the whole warm area.
(5) the ultraviolet-visible spectrum analysis that diffuses
Rare earth neodymium is replaced ZON structure phosphate aluminium molecular sieve UiO-7 carried out the ultraviolet-visible spectrum analysis that diffuses, the result sees Figure 32.Visible by Figure 32, strong absorption peak appears in ultraviolet region 200～300nm, show that Doped Rare Earth metal heteroatom Nd has entered into the skeleton of aluminium phosphate molecular sieve.And do not have absorption peak behind the 300nm, then can get rid of the existence of the outer heteroatoms oxide compound of skeleton.Can prove thus,, can prepare rare earth neodymium and replace ZON structure phosphate aluminium molecular sieve UiO-7 through the part aluminium atom on the isomorphous substitution framework of molecular sieve.
Embodiment 3
The ion hot preparation method that replaces ZON structure phosphate aluminium molecular sieve UiO-7 with Rare Earth Lanthanum is an example, and its step is following:
1, preparation eutectic mixture
It is identical that present embodiment prepares used raw material of the step 1 of eutectic mixture and proportioning and embodiment 1.Other step is identical with embodiment 1, is prepared into eutectic mixture, and using the fusing point appearance to survey fusing point is 54～56 ℃.
2, the preparation Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve Ui O-7 presoma
Used cerous nitrate is replaced with equimolar Lanthanum trinitrate, and other step in this step is identical with embodiment 1, and other step in this step is identical with embodiment 1, is prepared into Rare Earth Lanthanum and replaces ZON structure phosphate aluminium molecular sieve UiO7 presoma.
Other step is identical with embodiment 1, is prepared into Rare Earth Lanthanum and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Prepared Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7 and adopts X-ray diffractometer, N
2Diffuse spectrometer, thermal analyzer of absorption BET specific surface area appearance and aperture analyser, ultraviolet-visible characterizes the structure and the thermostability of molecular sieve; Environmental scanning electronic microscope has carried out observation experiment to the surface topography that Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7, and various experiment situation are following:
(1) X-ray diffraction analysis
The X-ray diffraction spectrogram of prepared product is as shown in Figure 3.Visible by Fig. 3, the X ray diffracting spectrum of the X ray diffracting spectrum of product and ZON structure phosphate aluminium molecular sieve UiO-7 is consistent, and crystalline percent crystallinity is higher.
(2) environmental scanning electronic microscope is observed
The stereoscan photograph of prepared product is seen Figure 15.Visible by Figure 12, Figure 15, UiO-7 compares with ZON structure phosphate aluminium molecular sieve, and it is spherical and mixture leaf shape that Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7 crystal, smooth surface, and crystalline structure is complete.
(3) measurement the specific area and pore volume
The SSA-4200 type N that Rare Earth Lanthanum is replaced ZON structure phosphate aluminium molecular sieve UiO-7 and the sale of ZON structure phosphate aluminium molecular sieve UiO-7 employing Beijing Bi Aode Electronic Arts Inc.
2Absorption BET specific surface area appearance and aperture analyser have carried out contrast test by the working method of instrument, and the specific surface area that Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7 is 248.6m
2/ g, pore volume are 0.185cc/g, and Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7 to be compared with ZON structure phosphate aluminium molecular sieve UiO-7, and specific surface area and pore volume that Rare Earth Lanthanum replaces ZON structure phosphate aluminium molecular sieve UiO-7 all increase to some extent.
(4) measure thermal stability
Rare Earth Lanthanum is replaced ZON structure phosphate aluminium molecular sieve UiO-7 adopt the U.S.'s Pyri s-of TA company II structural synthesis thermal analyzer (TG-DTA), test by the working method of instrument, test result is seen Figure 30.Rare Earth Lanthanum replaces the better heat stability of ZON structure phosphate aluminium molecular sieve UiO-7, and the crystalline structure is subsided when temperature is elevated to 600 ℃, has 2 main zero-g periods in the whole warm area.
(5) the ultraviolet-visible spectrum analysis that diffuses
Rare Earth Lanthanum is replaced ZON structure phosphate aluminium molecular sieve UiO-7 carried out the ultraviolet-visible spectrum analysis that diffuses, the result sees Figure 33.Visible by Figure 33, strong absorption peak appears in ultraviolet region 200～300nm, show that Doped Rare Earth metal heteroatom La has entered into the skeleton of aluminium phosphate molecular sieve.And do not have absorption peak behind the 300nm, then can get rid of the existence of the outer heteroatoms oxide compound of skeleton.Can prove thus,, can prepare Rare Earth Lanthanum and replace ZON structure phosphate aluminium molecular sieve UiO-7 through the part aluminium atom on the isomorphous substitution framework of molecular sieve.
Embodiment 4
In the preparation eutectic mixture step 1 of above embodiment 1～3; The 2.86g tetramethyl ammonium chloride is mixed in beaker with the 0.64g imidazoles; The mol ratio of tetramethyl ammonium chloride and imidazoles is 1:0.36, places the mortar ground and mixed even, and placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating; Be prepared into eutectic mixture, using the fusing point appearance to survey fusing point is 56～57 ℃.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:1.5:0.2:0.02 stirs in beaker; Move in the teflon-lined reaction kettle; 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Embodiment 5
In the preparation eutectic mixture step 1 of above embodiment 1～3; The 2.86g tetramethyl ammonium chloride is mixed in beaker with the 1.19g imidazoles; The mol ratio of tetramethyl ammonium chloride and imidazoles is 1:0.67, places the mortar ground and mixed even, and placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating; Be prepared into eutectic mixture, using the fusing point appearance to survey fusing point is 56～58 ℃.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:3:1.5:0.18 stirs in beaker; Move in the teflon-lined reaction kettle; 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Embodiment 6
In the preparation eutectic mixture step 1 of above embodiment 1～3; The 2.86g tetramethyl ammonium chloride is mixed in beaker with the 0.71g imidazoles; The mol ratio of tetramethyl ammonium chloride and imidazoles is 1:0.4; Place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:2.5:0.5:0.08 stirs in beaker; Move in the teflon-lined reaction kettle; 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Embodiment 7
In the preparation eutectic mixture step 1 of above embodiment 1～3; The 2.86g tetramethyl ammonium chloride is mixed in beaker with the 1.07g imidazoles; The mol ratio of tetramethyl ammonium chloride and imidazoles is 1:0.6; Place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:3:1.2:0.15 stirs in beaker; Move in the teflon-lined reaction kettle; 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Embodiment 8
The preparation eutectic mixture step 1 of above embodiment 1～7 is identical with respective embodiments, is prepared into eutectic mixture.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; Aluminum isopropylate is identical with the mol ratio and the respective embodiments of eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate; In beaker, stir, move in the teflon-lined reaction kettle 150 ℃ of crystallization of normal pressure 96 hours; Be cooled to room temperature, be prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Embodiment 9
The preparation eutectic mixture step 1 of above embodiment 1～7 is identical with respective embodiments, is prepared into eutectic mixture.
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step 2 at the preparation rare earth; Aluminum isopropylate is identical with the mol ratio and the respective embodiments of eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate; In beaker, stir, move in the teflon-lined reaction kettle 200 ℃ of crystallization of normal pressure 16 hours; Be cooled to room temperature, be prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
Other step is identical with embodiment 1, is prepared into rare earth and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
In order to confirm optimised process step of the present invention, the contriver has carried out a large amount of research trials, and the situation of various tests is following:
Experimental drug: tetramethyl ammonium chloride (analytical pure), imidazoles (analytical pure), aluminum isopropylate (analytical pure), phosphoric acid (85%, analytical pure), hydrofluoric acid (40%, CP), cerous nitrate (analytical pure), neodymium nitrate (CP), Lanthanum trinitrate (analytical pure).
Laboratory apparatus: Japanese Rigaku D/MAX-3C type X-ray powder diffraction appearance; The Quanta 200 type sem that Holland Phi l ipsFEI company produces.
1, confirms the consumption of rare earth nitrate
(1) confirms the consumption of cerous nitrate
Get and add 0.011g, 0.045g, 0.056g, 0.085g, 0.102g cerous nitrate in 5 groups of 3.75g eutectic mixtures respectively, in every group, add the 0.27g aluminum isopropylate respectively, 0.31g phosphoric acid; 0.026g hydrofluoric acid stirs, promptly the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, cerous nitrate is respectively 1:30:2:1:0.02; 1:30:2:1:0.08; 1:30:2:1:0.1,1:30:2:1:0.15,1:30:2:1:0.18; Move in the teflon-lined reaction kettle; Under normal pressure, 180 ℃ of crystallization 48 hours, be cooled to room temperature, be prepared into 5 kinds of rare earth ceriums and replace ZON structure phosphate aluminium molecular sieve UiO-7 presomas.Other step is identical with embodiment 1, is prepared into 5 kinds of rare earth ceriums and replaces ZON structure phosphate aluminium molecular sieve UiO-7.
Adopt X-ray diffractometer that structure is observed, X ray diffracting spectrum is seen Fig. 1, Fig. 4～Fig. 7.Visible by figure; Constant at other raw material consumption, the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, cerous nitrate is respectively 1:30:2:1:0.02,1:30:2:1:0.08; 1:30:2:1:0.1; 1:30:2:1:0.15 the X ray diffracting spectrum of the X-ray diffraction peak collection of illustrative plates of the product that 1:30:2:1:0.18 is prepared and ZON structure phosphate aluminium molecular sieve UiO-7 is consistent, belongs to preparation rare earth cerium and replaces ZON structure phosphate aluminium molecular sieve UiO-7 crystal.
Adopt environmental scanning electronic microscope that 5 kinds of rare earth ceriums replacement ZON structure phosphate aluminium molecular sieve UiO-7 surface topographies of preparation are observed, the environmental scanning electronic microscope photo is seen Figure 13, Figure 16～Figure 19.Visible by Figure 16, when the consumption of cerous nitrate is less when being 0.01g, ZON structure rare-earth heteroatoms phosphate aluminium molecular sieve is irregular bulk crystals; When the consumption of cerous nitrate is 0.05g (like Figure 17), the pattern that the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 changes, and obtains " being elongated " cubic column aggregate; Visible by Figure 19, the consumption of cerous nitrate is during to 0.11g, and the rare earth cerium replaces ZON structure phosphate aluminium molecular sieve UiO-7 crystal to be begun to take place to reunite but still keep cubic column pattern.
(2) confirm the consumption of neodymium nitrate
The influence that the consumption of neodymium nitrate replaces ZON structure phosphate aluminium molecular sieve UiO-7 to rare earth is shown in table 1, Fig. 2, Figure 14, Fig. 8～Figure 11, Figure 20～23.Increase the consumption of neodymium nitrate, begin to occur spherulite in the product, continue to increase the consumption of neodymium nitrate, spherulite is slowly grown up, smooth surface.The amount of neodymium nitrate is identical with the amount of cerous nitrate.
The consumption of table 1 neodymium nitrate replaces the influence of ZON structure phosphate aluminium molecular sieve Ui O-7 pattern and percent crystallinity to rare earth
| Sample | The quality of neodymium nitrate (g) | Crystallization temperature (℃) | Crystallization time (hour) | Surface | Percent crystallinity | |
| 1 | 0.011 | 180 | 48 | Leaf shape | 43.5 | |
| 2 | 0.046 | 180 | 48 | Leaf shape | 76.2 | |
| 3 | 0.057 | 180 | 48 | |
100 | |
| 4 | 0.085 | 180 | 48 | Leaf shape and spherical | 59.7 | |
| 5 | 0.103 | 180 | 48 | Leaf shape and spherical | 50.4 |
(3) confirm the consumption of Lanthanum trinitrate
The influence that the consumption of Lanthanum trinitrate replaces ZON structure phosphate aluminium molecular sieve UiO-7 to rare earth is shown in table 2, Figure 15, Figure 24～27.Increase the consumption of Lanthanum trinitrate, the leaf shape crystal in the mixture begins to change, and sharp-pointed two ends " polish " gradually, and the trend of piling up is layer by layer arranged.The Lanthanum trinitrate amount is identical with the amount of cerous nitrate.
The consumption of table 2 Lanthanum trinitrate replaces the influence of ZON structure phosphate aluminium molecular sieve UiO-7 pattern and percent crystallinity to rare earth
| Sample | The quality of Lanthanum trinitrate (g) | Crystallization temperature (℃) | Crystallization time (hour) | Surface | Percent crystallinity | |
| 1 | 0.011 | 180 | 48 | Leaf shape and spherical | 50.5 | |
| 2 | 0.045 | 180 | 48 | Leaf shape and spherical | 75.1 | |
| 3 | 0.056 | 180 | 48 | Leaf shape and spherical | 100 | |
| 4 | 0.084 | 180 | 48 | Pile up leaf shape layer by layer | 86.3 | |
| 5 | 0.101 | 180 | 48 | Pile up leaf shape layer by layer | 68.2 |
(4) confirm the consumption of phosphoric acid
Get and add 0.23g, 0.31g, 0.39g, 0.47g phosphoric acid in 4 groups of 3.75g eutectic mixtures respectively, in every group, add the 0.27g aluminum isopropylate respectively, 0.026g hydrofluoric acid; 0.056g cerous nitrate stirs, promptly the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, cerous nitrate is respectively 1:30:1.5:1:0.1; 1:30:2:1:0.1,1:30:2.5:1:0.1,1:30:3:1:0.1; Move in the teflon-lined reaction kettle; Under normal pressure, 180 ℃ of crystallization 48 hours, be cooled to room temperature, be prepared into 4 kinds of rare earth ceriums and replace ZON structure phosphate aluminium molecular sieve UiO-7 presomas.Other step is identical with embodiment 1, is prepared into 4 kinds of rare earth ceriums and replaces ZON structure phosphate aluminium molecular sieve UiO-7.Experiment and calculation result are seen table 3.
The consumption of table 3 phosphoric acid replaces the influence of ZON structure phosphate aluminium molecular sieve Ui O-7 pattern and percent crystallinity to the rare earth cerium
| Sample | The quality of phosphoric acid (g) | Crystallization temperature (℃) | Crystallization time (hour) | | Percent crystallinity | |
| 1 | 0.23 | 180 | 48 | CeUiO-7 | 84.6 | |
| 2 | 0.31 | 180 | 48 | Ce-UiO-7 | 100 | |
| 3 | 0.39 | 180 | 48 | Ce-UiO-7 | 93.4 | |
| 4 | 0.47 | 180 | 48 | Ce-UiO-7 | 86.7 |
(5) confirm the consumption of hydrofluoric acid
Get and add 0.005g, 0.013g, 0.026g, 0.031g, 0.039g hydrofluoric acid in 5 groups of 3.75g eutectic mixtures respectively, in every group, add the 0.27g aluminum isopropylate respectively, 0.31g phosphoric acid; 0.056g cerous nitrate stirs, promptly the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, cerous nitrate is respectively 1:30:2:0.2:0.1; 1:30:2:0.5:0.1; 1:30:2:1.0:0.1,1:30:2:1.2:0.1,1:30:2:1.5:0.1; Move in the teflon-lined reaction kettle; Under normal pressure, 180 ℃ of crystallization 48 hours, be cooled to room temperature, be prepared into 5 kinds of rare earth ceriums and replace ZON structure phosphate aluminium molecular sieve UiO-7 presomas.Other step is identical with embodiment 1, is prepared into 5 kinds of rare earth ceriums and replaces ZON structure phosphate aluminium molecular sieve UiO-7.Experiment and calculation result are seen table 4.
The consumption of table 4 hydrofluoric acid replaces the influence of ZON structure phosphate aluminium molecular sieve UiO-7 pattern and percent crystallinity to the rare earth cerium
| Sample | The quality of phosphoric acid (g) | Crystallization temperature (℃) | Crystallization time (hour) | | Percent crystallinity | |
| 1 | 0.005 | 180 | 48 | Ce-UiO-7 | 32.5 | |
| 2 | 0.013 | 180 | 48 | Ce-UiO-7 | 58.6 | |
| 3 | 0.026 | 180 | 48 | Ce-UiO-7 | 100 | |
| 4 | 0.031 | 180 | 48 | Ce-UiO-7 | 88.6 | |
| 5 | 0.039 | 180 | 48 | Ce-UiO-7 | 40.4 |
By above-mentioned; When the consumption of rare-earth heteroatoms Ce, Nd and La is respectively 0.011～0.102g, 0.011～0.103g and 0.011～0.101g; The mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that the prepared ZON structure rare-earth heteroatoms phosphate aluminium molecular sieve in 1:30:1.5～3:0.2～1.5:0.02～0.18 is formed with regular appearance; When wherein the mol ratio of aluminum isopropylate and phosphoric acid, hydrofluoric acid, rare earth nitrate is 1:2:1.0:0.1; The good dispersivity of molecular sieve crystal, uniform particles, percent crystallinity is high.It is 1:30:1～3:0.2～1.5:0.02～0.18 that the present invention selects the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate, and the optimum mole ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is 1:30:2:1.0:0.1.
2. confirm crystallization temperature
With Ce-UiO-7 is example; Get 4 groups of eutectic mixture 3.75g, aluminum isopropylate 0.27g, phosphoric acid 0.31g, hydrofluoric acid 0.026g, cerous nitrate 0.056g; The mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, cerous nitrate is 1:30:2:1:0.1; Stirring at room is even, moves in the teflon-lined reaction kettle, and be 150,160,180,200 ℃ of following crystallization 48 hours at crystallization temperature respectively; Be cooled to room temperature, be prepared into the rare earth cerium and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.Other step is identical with test 1, is prepared into the rare earth cerium and replaces ZON structure phosphate aluminium molecular sieve UiO-7.Calculate the percent crystallinity of prepared product, experiment and calculation result are seen table 5.
The different crystallization temperatures of table 5 replace the influence of ZON structure phosphate aluminium molecular sieve UiO-7 percent crystallinity to the rare earth cerium
| Sample | n Al 3+:n EU:n P 5+:n F -:n Ce 3+ | Crystallization temperature (℃) | Crystallization time (hour) | |
| 1 | 1:30:2:1:0.1 | 150 | 48 | 73.6 |
| 2 | 1:30:2:1:0.1 | 160 | 48 | 89.9 |
| 3 | 1:30:2:1:0.1 | 180 | 48 | 100 |
| 4 | 1:30:2:1:0.1 | 200 | 48 | 96.6 |
Can know that by table 5 along with the increase of temperature, the percent crystallinity of molecular sieve raises; When crystallization temperature was 180 ℃, percent crystallinity was the highest, and after this percent crystallinity begins to descend; The crystal crystallization temperature that rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7 is 150～200 ℃, and crystallization temperature the best is 180 ℃.
3, confirm crystallization time
Get 6 groups of eutectic mixtures, aluminum isopropylate, phosphoric acid, hydrofluoric acid, cerous nitrate; Consumption is identical with test 2, and mixture is stirred, and moves in the teflon-lined reaction kettle; Crystallization temperature is 180 ℃; Crystallization is 16,24,36,48,72,96 hours respectively, is cooled to room temperature, is prepared into the rare earth cerium and replaces ZON structure phosphate aluminium molecular sieve UiO-7 presoma.Other step is identical with test 1, is prepared into the rare earth cerium and replaces ZON structure phosphate aluminium molecular sieve UiO-7.Calculate the percent crystallinity of prepared product, experiment and calculation result are seen table 6.
The different crystallization times of table 6 are to the influence of ZON structure rare-earth heteroatoms phosphate aluminium molecular sieve percent crystallinity
| Sample | n A1 3+:n EU:n P 5+:n F -:n Ce 3+ | Crystallization temperature (℃) | Crystallization time (hour) | |
| 1 | 1:30:2:1:0.1 | 180 | 16 | 72.3 |
| 2 | 1:30:2:1:0.1 | 180 | 24 | 83.8 |
| 3 | 1:30:2:1:0.1 | 180 | 36 | 95.7 |
| 4 | 1:30:2:1:0.1 | 180 | 48 | 100 |
| 5 | 1:30:2:1:0.1 | 180 | 72 | 90.6 |
| 6 | 1:30:2:1:0.1 | 180 | 96 | 78.7 |
Visible by table 6; Crystallization time replaces ZON structure phosphate aluminium molecular sieve UiO-7 to rare earth and has certain influence, and along with the increase of temperature, the percent crystallinity of molecular sieve raises; After reaching 48 hours; Percent crystallinity begins to descend, and it is 16～96 hours that the present invention selects the time of crystallization, and best crystallization time is 48 hours.
Claims (3)
1. the ion hot preparation method of a rare earth replacement ZON structure phosphate aluminium molecular sieve U i O-7 is characterized in that it comprises the steps:
(1) preparation eutectic mixture
Tetramethyl ammonium chloride is mixed in beaker for 1:0.36～0.67 with imidazoles in molar ratio, place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture;
(2) the preparation rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7 presoma
With the mol ratio of aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate is that 1:30:1.5～3:0.2～1.5:0.02～0.18 stirs in beaker; Move in the teflon-lined reaction kettle; 150～200 ℃ of crystallization of normal pressure 16～96 hours; Be cooled to room temperature, be prepared into the hetero-atom molecular-sieve presoma;
Above-mentioned rare earth nitrate is any one in cerous nitrate, neodymium nitrate, the Lanthanum trinitrate;
(3) the preparation rare earth replaces ZON structure phosphate aluminium molecular sieve UiO-7
The molecular sieve presoma is filtered with B, use deionized water, ethanol, the ultrasonic repetitive scrubbing of acetone respectively 3～5 times, air-dry in the air, be prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7.
2. rare earth according to claim 1 replaces the ion hot preparation method of ZON structure phosphate aluminium molecular sieve Ui O-7; It is characterized in that: in preparation eutectic mixture step (1); Tetramethyl ammonium chloride is mixed in beaker for 1:0.4～0.6 with imidazoles in molar ratio; Place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture;
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step (2) at the preparation rare earth; Aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate are stirred in beaker for 1:30:1.5～2.5:0.5～1.2:0.08～0.15 in molar ratio; Move in the teflon-lined reaction kettle; 160～180 ℃ of crystallization of normal pressure 24～72 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
3. rare earth according to claim 1 replaces the ion hot preparation method of ZON structure phosphate aluminium molecular sieve UiO-7, it is characterized in that: in preparation eutectic mixture step (1), be 1:0.5 in molar ratio with tetramethyl ammonium chloride and imidazoles; In beaker, mix, place the mortar ground and mixed even, placing the interior vacuum tightness of vacuum drying oven is 0.09MPa, 60 ℃ of heating, is prepared into eutectic mixture;
Replace in the ZON structure phosphate aluminium molecular sieve UiO-7 presoma step (2) at the preparation rare earth; Aluminum isopropylate and eutectic mixture, phosphoric acid, hydrofluoric acid, rare earth nitrate are stirred in beaker for 1:30:2:1.0:0.1 in molar ratio; Move in the teflon-lined reaction kettle; 180 ℃ of crystallization of normal pressure 48 hours are cooled to room temperature, are prepared into rare earth and replace ZON structure phosphate aluminium molecular sieve UiO-7 presoma.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
| CN101486473A (en) * | 2009-02-20 | 2009-07-22 | 陕西师范大学 | Microwave preparation of AEL structure zinc-phosphor-aluminum molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| CN101269821A (en) * | 2008-05-07 | 2008-09-24 | 中国科学院过程工程研究所 | Ion thermal method for preparing molecular sieve in alcohol amine ion liquid |
| CN101486473A (en) * | 2009-02-20 | 2009-07-22 | 陕西师范大学 | Microwave preparation of AEL structure zinc-phosphor-aluminum molecular sieve |
Non-Patent Citations (1)
| Title |
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| 侯静雯等: "UiO-7分子筛的离子热合成", 《第八届全国工业催化技术及应用年会论文集》 * |
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